US4990473A - Zirconyl phosphate ceramics, a process for their production and their use - Google Patents
Zirconyl phosphate ceramics, a process for their production and their use Download PDFInfo
- Publication number
- US4990473A US4990473A US07/364,845 US36484589A US4990473A US 4990473 A US4990473 A US 4990473A US 36484589 A US36484589 A US 36484589A US 4990473 A US4990473 A US 4990473A
- Authority
- US
- United States
- Prior art keywords
- zirconyl phosphate
- weight
- zirconyl
- antimony
- ceramics
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 46
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 42
- 239000010452 phosphate Substances 0.000 title claims abstract description 42
- 239000000919 ceramic Substances 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims description 12
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 235000021317 phosphate Nutrition 0.000 claims abstract description 45
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 238000005245 sintering Methods 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 9
- 230000035939 shock Effects 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 7
- 150000001463 antimony compounds Chemical class 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical class [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 claims abstract description 5
- 238000002485 combustion reaction Methods 0.000 claims abstract description 4
- 238000000465 moulding Methods 0.000 claims abstract description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 10
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 10
- 229910000410 antimony oxide Inorganic materials 0.000 claims description 9
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims description 9
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 4
- 230000002035 prolonged effect Effects 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 2
- 229910010293 ceramic material Inorganic materials 0.000 claims 2
- AHBGXHAWSHTPOM-UHFFFAOYSA-N 1,3,2$l^{4},4$l^{4}-dioxadistibetane 2,4-dioxide Chemical compound O=[Sb]O[Sb](=O)=O AHBGXHAWSHTPOM-UHFFFAOYSA-N 0.000 claims 1
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 4
- 238000005056 compaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910017895 Sb2 O3 Inorganic materials 0.000 description 2
- 229910017969 Sb2 O4 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229910017966 Sb2 O5 Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000007952 growth promoter Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052914 metal silicate Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/06—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances
- C04B38/063—Preparing or treating the raw materials individually or as batches
- C04B38/0635—Compounding ingredients
- C04B38/0645—Burnable, meltable, sublimable materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/14—Other self-supporting filtering material ; Other filtering material
- B01D39/20—Other self-supporting filtering material ; Other filtering material of inorganic material, e.g. asbestos paper, metallic filtering material of non-woven wires
- B01D39/2068—Other inorganic materials, e.g. ceramics
- B01D39/2072—Other inorganic materials, e.g. ceramics the material being particulate or granular
- B01D39/2075—Other inorganic materials, e.g. ceramics the material being particulate or granular sintered or bonded by inorganic agents
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/447—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on phosphates, e.g. hydroxyapatite
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00793—Uses not provided for elsewhere in C04B2111/00 as filters or diaphragms
Definitions
- This invention relates to zirconyl phosphate ceramics of high strength and high heat shock resistance, to a process for their production and to their use.
- powder mixtures capable of compaction to ceramics of low thermal expansion and high strength by sintering at 1200° to 1700° C. can be produced from mixtures of zirconyl phosphate with compaction aids, such as magnesium oxide, zinc oxide, bismuth oxide, manganese oxide, iron oxide, cobalt oxide, nickel oxide, titanium oxide, cerium oxide, niobium oxide, tantalum oxide or mixtures of these oxides.
- compaction aids such as magnesium oxide, zinc oxide, bismuth oxide, manganese oxide, iron oxide, cobalt oxide, nickel oxide, titanium oxide, cerium oxide, niobium oxide, tantalum oxide or mixtures of these oxides.
- grain growth promoters such as SiO 2 or metal silicates
- melts of metal orthophosphates are formed during the sintering process, enabling the zirconyl phosphate to be compacted.
- the ceramics formed are thus all multiple-phase ceramics which means that in addition to ⁇ -zirconyl phosphate, other substances are present in the materials in quantities of more than 1%.
- the object of the present invention is to provide zirconyl phosphate ceramics which do not have any of the decribed disadvantages.
- zirconyl phosphate ceramics obtained by sintering zirconyl phosphate compacts in the presence of antimony-containing compounds consist almost entirely of phosphates of zirconium.
- ceramics according to the present invention have high stability of their strength values after prolonged exposure to high temperatures and are highly heat-shock-resistant. As such, the ceramics of this invention are highly useful in filters and as the fabrication material for internal combustion engine parts.
- the ceramics of the present invention are zirconyl phosphate ceramics which consist essentially of at least 99% by weight of zirconyl phosphates, zirconium phosphates or both and no other phase material in quantities of more than 1% by weight.
- the present invention relates to zirconyl phosphate ceramics of high strength and high heat shock resistance which, apart from zirconyl and/or zirconium phosphates, contain no other phase in quantities above 1% by weight. They preferably have antimony contents of less than 0.5% by weight. In a particularly preferred embodiment, the antimony contents are less than 0.1% by weight. Accordingly, the ceramics according to the invention are high-purity zirconyl phosphate ceramics with no foreign binding phases which combine adequate flexural strength with heat shock resistance and, at the same time, show good long-term strength. In one preferred embodiment, the flexural strength values are >20 N/mm 2 .
- the zirconyl phosphate cerramics according to the invention may be obtained by carrying out their production in the presence of antimony compounds.
- antimony compounds are added to zirconyl phosphate or to substances which form phosphate under the reaction conditions and powder compacts are obtained from this material by sintering.
- the antimony compounds are Sb 2 O 3 , Sb 2 O 5 and/or Sb 2 O 4 or compounds which form these oxides on heating.
- the present invention also relates to a process for the production of zirconyl phosphate ceramics of high strength and high heat shock resistance, characterized in that zirconyl phosphate and/or substances which form zirconyl phosphate under the reaction conditions are mixed with antimony compounds, the resulting mixture is then molded and sintered at temperatures of 1200° to 1700° C.
- the antimony oxide content of the compacts before sintering is preferably between 4 and 30% by weight, expressed as antimony oxide.
- the antimony oxides are almost completely evaporated during sintering. To obtain particularly high-quality products, it is of advantage to sinter the described mixtures until all or almost all the antimony oxide has evaporated. After sintering, there are only traces of antimony oxide, if any, in the ceramics.
- zirconyl phosphate and/or substances which form zirconyl phosphate are presynthesized by mixing and calcining to antimony-containing zirconyl phosphate. After suitable grinding, optionally mixing with non-pre-synthesized material molding and sintering, substantially antimony-free ceramics having strengths of more than 60 N/mm 2 are obtained.
- the ceramics produced in accordance with the invention show high stability of their strength values after prolonged exposure to temperatures of the type encountered in practical applications.
- the ceramics are heat-shock-resistant and even local heating with a cutting torch to white heat does not destroy the material. No reduction in strength was observed after such treatments.
- the present invention also relates to the use of the zirconyl phosphate ceramics according to the invention as ceramic filters or as components of internal combustion engines, for example as port liners.
- cerramic platelets 500 g of a ⁇ -zirconyl phosphate powder, grain size ⁇ 10 ⁇ m, were mixed with 50 g of S b 2O 3 (about 9% by weight) compressed to 5 mm thick tablets and calcined for 4 hours at 1400° C.
- the cerramic platelets obtained were removed from the hot furnace and quenched. They had a flexural strength of 21 N/mm 2 , an open porosity of 14% and a coefficient of thermal expansion of 1 ⁇ 10 -6 /K for the temperature range from 20° to 1000° C. with a substantially linear trend and a very narrow hysteresis curve.
- Example 1 100 g Sb 2 O 3 were added to 500 g ⁇ -zirconyl phosphate and the resulting mixture was compressed to tablets and calcined at 1200° C.
- the product formed which contained 15.1% Sb 2 O 4 , was reduced to a grain size of less than 63 ⁇ m in a disc vibration mill, compressed to tablets and sintered as in Example 1.
- the ceramic had a flexural strength of 60 N/mm 2 for a porosity of 6% and a coefficient of thermal expansion of 1.2 ⁇ 10 -6 /K with a substantially linear trend and a very narrow hysteresis curve.
- Disc-form ceramics 4.5 cm in diameter produced in accordance with Examples 1 and 2 were tempered for 168 hours at 1400° C. No reduction in strength was observed. The ceramics showed such high resistance to heat shock that plates which had been heated to 1400° C. could be quenched in cold water without shattering.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Glass Compositions (AREA)
- Materials For Medical Uses (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3820961A DE3820961C1 (enExample) | 1988-06-22 | 1988-06-22 | |
| DE3820961 | 1988-06-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US4990473A true US4990473A (en) | 1991-02-05 |
Family
ID=6356944
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US07/364,845 Expired - Fee Related US4990473A (en) | 1988-06-22 | 1989-06-12 | Zirconyl phosphate ceramics, a process for their production and their use |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US4990473A (enExample) |
| EP (1) | EP0347667A3 (enExample) |
| JP (1) | JPH02120270A (enExample) |
| DE (1) | DE3820961C1 (enExample) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4703023A (en) * | 1985-03-22 | 1987-10-27 | Nihon Ceramics Co., Ltd. | Process for the production of low-thermal-expansive (ZrO)2 P2 O7 ceramic |
-
1988
- 1988-06-22 DE DE3820961A patent/DE3820961C1/de not_active Expired
-
1989
- 1989-06-09 EP EP19890110460 patent/EP0347667A3/de not_active Withdrawn
- 1989-06-12 US US07/364,845 patent/US4990473A/en not_active Expired - Fee Related
- 1989-06-19 JP JP1154789A patent/JPH02120270A/ja active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4703023A (en) * | 1985-03-22 | 1987-10-27 | Nihon Ceramics Co., Ltd. | Process for the production of low-thermal-expansive (ZrO)2 P2 O7 ceramic |
Non-Patent Citations (2)
| Title |
|---|
| Yamai et al., "Low-Thermal-Expansion Polycrystalline Zirconyl Phosphate Ceramic", J. American Soc. 68 [5] 73-78, 1985. |
| Yamai et al., Low Thermal Expansion Polycrystalline Zirconyl Phosphate Ceramic , J. American Soc. 68 5 73 78, 1985. * |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3820961C1 (enExample) | 1989-08-10 |
| EP0347667A2 (de) | 1989-12-27 |
| JPH02120270A (ja) | 1990-05-08 |
| EP0347667A3 (de) | 1990-09-19 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AS | Assignment |
Owner name: BAYER AKTIENGESELLSCHAFT, GERMANY Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:GUGEL, ERNST;PETZENHAUSER, ISFRIED;REEL/FRAME:005089/0743 Effective date: 19890524 Owner name: LOEVENICH & COMP., GERMANY Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:GUGEL, ERNST;PETZENHAUSER, ISFRIED;REEL/FRAME:005089/0743 Effective date: 19890524 |
|
| REMI | Maintenance fee reminder mailed | ||
| LAPS | Lapse for failure to pay maintenance fees | ||
| FP | Lapsed due to failure to pay maintenance fee |
Effective date: 19950208 |
|
| STCH | Information on status: patent discontinuation |
Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362 |